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EP0465263B1 - Polysiléthylènesiloxane - Google Patents

Polysiléthylènesiloxane Download PDF

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Publication number
EP0465263B1
EP0465263B1 EP91306117A EP91306117A EP0465263B1 EP 0465263 B1 EP0465263 B1 EP 0465263B1 EP 91306117 A EP91306117 A EP 91306117A EP 91306117 A EP91306117 A EP 91306117A EP 0465263 B1 EP0465263 B1 EP 0465263B1
Authority
EP
European Patent Office
Prior art keywords
group
polysilethylenesiloxane
carbon atoms
perfluoroalkylethyl
hydrocarbon group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91306117A
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German (de)
English (en)
Other versions
EP0465263A3 (en
EP0465263A2 (fr
Inventor
Toshio Takago
Hirofumi Kishita
Hitoshi Kinami
Kenichi Fukuda
Shinichi Sato
Koichi Yamaguchi
Shuji Suganuma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP17873090A external-priority patent/JPH0615616B2/ja
Priority claimed from JP17873290A external-priority patent/JPH0615618B2/ja
Priority claimed from JP2178728A external-priority patent/JPH0662773B2/ja
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of EP0465263A2 publication Critical patent/EP0465263A2/fr
Publication of EP0465263A3 publication Critical patent/EP0465263A3/en
Application granted granted Critical
Publication of EP0465263B1 publication Critical patent/EP0465263B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/485—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

  • the present invention relates to a novel polysilethylenesiloxane.
  • Dimethylpolysiloxanes are excellent in heat resistance, cold resistance, and weather resistance and also excellent in properties such as elastomeric properties, release properties, and electrical properties and are used in wide fields as a major component, for example, in various rubber materials and coating materials for building materials, transport equipment, household electrical appliances, business and office machines, etc. These properties of dimethylpolysiloxanes are ascribed to the facts that the bond energy of the siloxane linkage constituting the backbone chain is high, the siloxane linkage is ionic, and the intermolecular cohesive force of the siloxane molecule is small.
  • dimethylpolysiloxanes have such defects as that the backbone chain is liable to be cleaved by an ionic agent such acids and alkalis and the mechanical strength properties are not satisfactory.
  • an object of the present invention is to provide a novel polysiloxane compound which obviates the above defects possessed by dimethylpolysiloxanes.
  • the present polysilethylenesiloxane is represented by the following general formula [I]: wherein R 1 and R 2 , which may be the same or different, each represent a hydrocarbon group having 1 to 10 carbon atoms, R 3 and R 4 , which may be the same or different, each represent a hydrocarbon group having 1 to 10 carbon atoms or a perfluoroalkylethyl group, represented by the formula -CH 2 CH 2 C m F 2m+1 , wherein m is a positive integer of from 4 to 10 and at least one of R 3 and R 4 represents the perfluoroalkylethyl group, and n is an integer of 10 to 1,000.
  • the present invention has succeeded in obviating the above defects possessed by dimethylpolysiloxanes.
  • Fig. 1 is a GPC chart of the polymer synthesized in Example 1.
  • Fig. 2 is a diagram showing the infrared absorption spectrum of the polymer synthesized in Example 1.
  • Fig. 3 is a GPC chart of the polymer synthesized in Example 2.
  • Fig. 4 is a diagram showing the infrared absorption spectrum of the polymer synthesized in Example 2.
  • R 1 and R 2 each represent a hydrocarbon group having 1 to 10 carbon atoms, for example, a lower alkyl group having up to 8 carbon atoms such as a methyl group, an ethyl group, and a propyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, and an isopropenoxy group, an aryl group such as a phenyl group, a tolyl group, and a naphthyl group, and an aralkyl group such as a benzyl group and a 2-phenylethyl group.
  • R 1 and R 2 may be the same or different.
  • the most preferable group in the present invention is a lower alkyl group, particularly a methyl group.
  • R 3 and R 4 each represent a hydrocarbon group having 1 to 10 carbon atoms or a perfluoroalkylethyl group.
  • the hydrocarbon group includes those exemplified for R 1 and R 2 and, among them, a preferable hydrocarbon group is a lower alkyl group having up to 8 carbon atoms and the most preferable hydrocarbon group is a methyl group.
  • the perfluoroalkylethyl group is one represented by the following formula: -CH 2 CH 2 C m F 2m+1 , wherein m is a positive integer of 4 to 10 such as C 4 F 9 CH 2 CH 2 -, C 6 F 13 CH 2 CH 2 -, C 8 F 17 CH 2 CH 2 -, and C 10 F 21 CH 2 CH 2 -.
  • n is an integer of 10 to 1,000, and due to such a value of n the present polysilethylenesiloxane has a viscosity at 25 °C in the range of 25 to 500,000 cSt, preferably 1,000 to 100,000 cSt.
  • the present polysilethylenesiloxane can be synthesized in various manners, typically it can be synthesized by the ring opening polymerization of a 5-membered cyclic silethylenesiloxane represented by the following general formula [III]: wherein R 1 to R 4 have the meanings defined above, obtained by hydrolyzing a dichlorosilane represented by the following general formula [II]: wherein R 1 to R 4 have the meanings defined above.
  • the ring open polymerization is generally carried out by heating in the presence of a polymerization catalyst.
  • the heating temperature is suitably 10 to 200 °C.
  • a polymerization catalyst a hydroxide and a silanolate of an alkali metal such as lithium, potassium, and sodium is suitably used and also an acid catalyst, an alkali catalyst, and the like used in the conventional ring open polymerization of dimethylpolysiloxanes may be used. It is preferable that such a polymerization catalyst is used generally in an amount of 0.001 to 1 part by weight per 100 parts by weight of the 5-membered cyclic silethylenesiloxane although the amount varies depending on the type of the polymerization catalyst.
  • the present polysilethylenesiloxane prepared in this way is a liquid polymer quite useful as a major component of an elastomer composition excellent in properties such as chemical resistance, water repellency, and electrical properties and high in strength and elongation.
  • a rubber cured product having the above properties can be obtained.
  • the polysilethylenesiloxane of the present invention can provide a rubber cured product low in swelling in organic solvents and machine oils and improved in releasability, water repellency, and oil repellency.
  • the present polysilethylenesiloxane is expected to be used as a raw material for coating materials or rubber materials which are highly functional.
  • reaction mixture was cooled to room temperature and was filtered under pressure and the filtrate was stripped by an evaporator at 100 °C for 2 hours under a pressure for 3 mmHg to obtain 116 g of a viscous oil.
  • Measuring equipment GLC-8020 manufactured by Tosoh K.K.
  • reaction mixture was cooled to room temperature and was filtered under pressure and the filtrate was stripped by an evaporator at 100 °C for 2 hours under a pressure of 3 mmHg to obtain 108 g of a viscous oil.
  • Measuring equipment HLC-8020 manufactured by Tosoh K.K.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Claims (5)

  1. Polysiléthylènesiloxane représenté par la formule générale (I) ci-dessous:
    Figure imgb0014
     dans laquelle R1 et R2, qui peuvent être identiques ou différents, représentent chacun un groupe hydrocarboné ayant de 1 à 10 atomes de carbone, R3 et R4, qui peuvent être identiques ou différents, représentent chacun un groupe hydrocarboné ayant de 1 à 10 atomes de carbone ou un groupe perfluoroalkyléthyle représenté par les formules -CH2CH2CmF2m+1, où m est un nombre entier positif choisi de 4 à 10 et au moins un des radicaux R3 et R4 représente le groupe perfluoroalkyléthyle, et n est un nombre entier choisi de 10 à 1000.
  2. Polysiléthylènesiloxane tel que revendiqué dans la revendication 1, dans lequel ledit groupe hydrocarboné est un groupe alkyle inférieur comportant jusqu'à 8 atomes de carbone.
  3. Polysiléthylènesiloxane tel que revendiqué dans la revendication 2, dans lequel ledit groupe hydrocarboné est un groupe méthyle.
  4. Polysiléthylènesiloxane tel que revendiqué dans la revendication 1, dans lequel, dans ladite formule générale (I), R3 et R4 représentent chacun un groupe perfluoroalkyléthyle.
  5. Polysiléthylènesiloxane tel que revendiqué dans l'une quelconque des revendications 1 à 4 dans lequel ledit groupe perfluoroalkyléthyle est choisi dans le groupe constitué par C4F9CH2CH2-, C6F13CH2CH2-, C8F17CH2CH2- et C10F21CH2CH2-.
EP91306117A 1990-07-06 1991-07-05 Polysiléthylènesiloxane Expired - Lifetime EP0465263B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP178730/90 1990-07-06
JP17873090A JPH0615616B2 (ja) 1990-07-06 1990-07-06 含フッ素ポリシルエチレンシロキサン
JP17873290A JPH0615618B2 (ja) 1990-07-06 1990-07-06 含フッ素ポリシルエチレンシロキサン
JP178728/90 1990-07-06
JP178732/90 1990-07-06
JP2178728A JPH0662773B2 (ja) 1990-07-06 1990-07-06 ポリシルエチレンシロキサン

Publications (3)

Publication Number Publication Date
EP0465263A2 EP0465263A2 (fr) 1992-01-08
EP0465263A3 EP0465263A3 (en) 1992-09-09
EP0465263B1 true EP0465263B1 (fr) 1996-10-09

Family

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EP91306117A Expired - Lifetime EP0465263B1 (fr) 1990-07-06 1991-07-05 Polysiléthylènesiloxane

Country Status (3)

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US (1) US5117025A (fr)
EP (1) EP0465263B1 (fr)
DE (1) DE69122559T2 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0517489A (ja) * 1991-07-04 1993-01-26 Shin Etsu Chem Co Ltd シロキサン化合物
JP2636616B2 (ja) * 1991-12-12 1997-07-30 信越化学工業株式会社 室温硬化性シリコーンゴム組成物及びその硬化物
JPH05222066A (ja) * 1992-02-17 1993-08-31 Shin Etsu Chem Co Ltd 新規有機ケイ素化合物
JP3368005B2 (ja) * 1993-08-26 2003-01-20 東レ・ダウコーニング・シリコーン株式会社 消泡剤組成物
JPH0770324A (ja) * 1993-09-03 1995-03-14 Toray Dow Corning Silicone Co Ltd 有機ケイ素重合体の製造方法
JPH07216092A (ja) * 1994-01-27 1995-08-15 Toray Dow Corning Silicone Co Ltd 有機ケイ素交互共重合体およびその製造方法
JP3452978B2 (ja) * 1994-04-28 2003-10-06 東レ・ダウコーニング・シリコーン株式会社 両末端官能性有機ケイ素重合体の製造方法
JPH0812762A (ja) * 1994-06-29 1996-01-16 Toray Dow Corning Silicone Co Ltd 含フッ素有機ケイ素重合体およびその製造方法
JPH0841206A (ja) * 1994-07-26 1996-02-13 Toray Dow Corning Silicone Co Ltd 有機ケイ素重合体およびその製造方法
JPH0859839A (ja) * 1994-08-18 1996-03-05 Toray Dow Corning Silicone Co Ltd 含フッ素有機ケイ素共重合体
JPH0873809A (ja) * 1994-08-31 1996-03-19 Toray Dow Corning Silicone Co Ltd 剥離性皮膜形成性有機ケイ素重合体組成物
US6080829A (en) 1998-06-24 2000-06-27 Medtronic, Inc. Silalkylenesiloxane copolymer materials and methods for their preparation
EP1164156B1 (fr) * 1999-10-28 2006-12-06 Japan Science and Technology Agency Procede de polymerisation de silalkylenesiloxanes
US6524716B2 (en) * 2000-07-27 2003-02-25 The Goodyear Tire & Rubber Company Method for the preparation of a diene polymer interpenetrated with a polysiloxane
US6458461B1 (en) 2000-12-06 2002-10-01 Lexmark International, Inc Release agent composition
JP2013510079A (ja) 2009-11-03 2013-03-21 ダウ コーニング コーポレーション ポリシルアルキレンシロキサンの製造プロセス
JP5788852B2 (ja) * 2011-11-01 2015-10-07 信越化学工業株式会社 フルオロオキシアルキレン基含有ポリマー組成物、該組成物を含む表面処理剤、該表面処理剤で処理された物品及び光学物品
JP6355821B2 (ja) * 2014-04-25 2018-07-11 ノバルティス アーゲー カルボシロキサンビニル系モノマー

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041362A (en) * 1959-08-14 1962-06-26 Dow Corning Cyclic silethylenesiloxanes and polymers thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2562000A (en) * 1946-10-28 1951-07-24 Du Pont Polyarylene-siloxanes and processes for making same
US2732390A (en) * 1954-09-09 1956-01-24 Salts of organosilanols
GB773175A (en) * 1954-09-09 1957-04-24 Midland Silicones Ltd Salts of organosilanols
US3294740A (en) * 1965-01-25 1966-12-27 Dow Corning Method of polymerizing cyclotrisiloxanes ii

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041362A (en) * 1959-08-14 1962-06-26 Dow Corning Cyclic silethylenesiloxanes and polymers thereof

Also Published As

Publication number Publication date
DE69122559D1 (de) 1996-11-14
EP0465263A3 (en) 1992-09-09
EP0465263A2 (fr) 1992-01-08
DE69122559T2 (de) 1997-03-13
US5117025A (en) 1992-05-26

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